The present invention relates to cosmetic and/or dermatological compositions for artificially coloring the skin, comprising, for example, in a cosmetically acceptable support; at least one self-tanning agent chosen from monocarbonyl compounds and polycarbonyl compounds and at least one flavylium salt compound which is unsubstituted in position 3, which is substituted with at least one radical chosen from hydroxyl and alkoxy radicals, wherein the at least one flavylium salt compound may be obtained, for example, in a manner chosen from synthetically, from a plant extract containing it, and from an enriched plant extract containing it.
The invention also relates to the use of the composition for coloring the skin.
Nowadays, it is important to look healthy, and a tanned skin is always a sign of good health. However, a natural tan may not always be desirable since it requires long exposure to UV radiation, for example to UV-A radiation which causes the tanning of the skin. UV-A radiation is also liable to induce an adverse change of the skin, for example in the case of sensitive skin or skin which is continually exposed to solar radiation. It may thus be desirable to find an alternative to a natural tan which may be compatible with the requirements of such skin types.
Most of the cosmetic products intended for artificially tanning the skin are based on monocarbonyl and polycarbonyl compounds which, by interacting with the amino acids in the skin, allow the formation of colored products.
To this end, it is known that dihydroxyacetone, or DHA, is a product which is commonly used in cosmetics as an agent for artificially tanning the skin. When applied to the skin, for example to the face, it gives a tanning or bronzing effect which may be similar in appearance to that which may result from prolonged exposure to sunlight (a natural tan) or under a UV lamp.
One drawback of DHA can be the length of time the coloration takes to develop. Specifically, several hours (3 to 5 hours in general) may be required for the coloration to be revealed. Furthermore, the coloration produced on the skin by DHA may often be considered as too yellow by users.
Thus, efforts are still under way to find novel compounds and novel compositions which can give the skin an artificial coloration, for example, close to that of a natural tan, in at least one of a simple, effective, fast, and risk-free manner.
Anthocyanin colorants have been known for a long time as pharmaceutical and food colorants. These anthocyans may be present in nature in the form of heterosides known as anthocyanosides and genins, known as anthocyanidines. These anthocyans may be phenyl-2-benzopyrylium derivatives and flavylium derivatives and may be present, for example, in the plant in the form of salts. Anthocyans may be red-, violet- or blue-colored compounds which generally color flowers, fruit, and occasionally leaves. The color observed may depend both on the structure of the predominant genin and on the conditions of the medium in which the anthocyanin colorants are present.
Now, after considerable research conducted in the field of artificial coloring of the skin, the Inventors have discovered that the combination of at least one self tanning agent chosen from monocarbonyl compounds and polycarbonyl compounds, for example DHA, and at least one flavylium salt compound unsubstituted in position 3, may give the skin, after the product has been applied thereto, an artificial coloration, for example, a coloration close to that of a natural tan. Specifically, the Inventors have found that the combination may make it possible to obtain, compared with a self-tanning agent of the carbonyl type for example DHA used alone, an increase in color on the skin in a much shorter time (for example after 30 minutes). Furthermore, the combination may make it possible to obtain a shade which may be close to that of a natural tan and which may be stable over time.
One subject of the present invention is thus a novel cosmetic and/or dermatological composition for giving the skin an artificial coloration, for example, close to that of a natural tan, comprising, for example, in a cosmetically acceptable support, at least one self-tanning agent chosen from monocarbonyl compounds and polycarbonyl compounds, and at least one flavylium salt compound which is unsubstituted in position 3 and which is substituted with at least one radical chosen from hydroxyl and alkoxy radicals, wherein the at least one flavylium salt compound may be, for example, obtained in a manner chosen from synthetically, from a plant extract containing it, and from an enriched plant extract containing it.
A subject of the present invention is also the novel use of the combination of at least one self-tanning agent chosen from a monocarbonyl compound and a polycarbonyl compound, and at least one flavylium salt compound which is unsubstituted in position 3 and which is substituted with at least one radical chosen from hydroxyl and alkoxy radicals, for example, obtained in a manner chosen from synthetically, from a plant extract containing it, and from an enriched plant extract containing it, in cosmetic and/or dermatological compositions, with the aim of giving the skin an artificial coloration, for example, close to that of a natural tan.
A subject of the present invention is also a process for giving the skin an artificial coloration, for example, close to that of a natural tan, comprising applying to the skin an effective amount of a combination of at least one self-tanning agent chosen from monocarbonyl compounds and polycarbonyl compounds, and at least one flavylium salt compound which is unsubstituted in position 3 and which is substituted with at least one radical chosen from hydroxyl and alkoxy radicals, obtained, for example, in a manner chosen from synthetically, from a plant extract, and from an enriched plant extract, in a cosmetic composition.
The composition and uses in accordance with the invention may make it possible to obtain an artificial coloration, for example, close to that of a natural tan, in a very short space of time. Thus, an immediate coloration may be obtained, which may allow at least one of the following properties: visualization of the application, and better homogeneity in the spreading of the composition on the skin and thus of the resulting coloration. Furthermore, the artificial coloration obtained on the skin according to the invention may be extremely close to that of a natural tan.
For the purposes of the present invention, the expression xe2x80x9ccomposition intended for artificially coloring the skinxe2x80x9d will be understood to mean a formulation with a particular affinity for the skin which allows it to give the skin a long-lasting coloration. The formulation may be at least one of non-covering (does not have a tendency to opacify the skin), not removed either with water or with a solvent, and able to withstand both rubbing and washing with a solution containing surfactants. Such a long-lasting coloration may thus be distinguished from the superficial and transient coloration provided, for example, by a make-up product.
Other characteristics, aspects and advantages of the present invention, at least one of which may be present in a specific embodiment, will become apparent on reading the detailed description which follows.
For example, the composition, in accordance with the present invention, may, for example, generally lead, 30 minutes after application to a fair skin at a rate of 2 mg/cm2, to a darkening characterized in the (L*, a*, b*) calorimetric measuring system by a xcex94L* ranging from xe2x88x920.5 to xe2x88x9220. For example, xcex94L* may range from xe2x88x920.5 to xe2x88x9215.
For example, the composition, in accordance with the present invention, may give, 30 minutes after application to the skin at a rate of 2 mg/cm2, a coloration on a fair skin which may be defined in the (L*, a*, b*) colorimetric measuring system, by a ratio xcex94a*/xcex94b* ranging from 0.5:1:3:1, and for example ranging from 0.8:1:2:1.
According to the present invention, the term xe2x80x9cfair skinxe2x80x9d should be understood to indicate an untanned skin whose calorimetric characteristics may be defined by its ITA angle as defined in the publication by A. Chardon et al. xe2x80x9cSkin Color Typology and Suntanning Pathwaysxe2x80x9d presented at the 16th IFSCC congress, Oct. 8-10, 1990, New York, and in Int. J. Cosm. Sci. 13 191-208 (1991), the disclosures of both references relating to such calorimetric characteristics are hereby incorporated by reference. The fair skin as defined in this classification may have an ITA angle ranging from 35 to 55.
In the (L*, a*, b*) calorimetric measuring system: L* is luminance or clarity, a* is the red-green axis (xe2x88x92a*=green, +a*=red) and b* is the yellow-blue axis (xe2x88x92b*=blue, +b*=yellow). Thus, a* and b* express the shade of the skin.
xcex94L* reflects the darkening of the color: the more negative the xcex94L*, the darker the color becomes, with: xcex94L*=L* uncolored skinxe2x88x92L* colored skin
The ratio xcex94a*/xcex94b* reflects the red/yellow balance and thus the shade, with:
xcex94a*=a* uncolored skinxe2x88x92a* colored skin
xcex94b*=b* uncolored skinxe2x88x92b* colored skin
The at least one flavylium salt compound which may be unsubstituted in position 3, in accordance with the invention, which may, for example, be used are those corresponding to formula (I) below: 
wherein:
R1 is chosen from an OH radical and linear and branched, saturated and unsaturated (C1-C8) alkoxy radicals,
R2, R3 and R4, which may be identical or different, are chosen from H and R1,
it being understood that, for example, in one embodiment of the invention, at least one of the radicals R1 to R4 is OH,
Xxe2x80x94 is chosen from organic anions, mineral anions, and for example, from mineral acid derivatives chosen from, for example, halides, for example bromide and chloride; and organic acid derivatives chosen from, for example, acetate, borate, citrate, tartrate, lactate, bisulphate, sulphate, and phosphate.
The at least one flavylium salt compound of formula (I) may be, according to the present invention, chosen from a group for which, in formula (I), R1 is chosen from OH and OCH3.
Among these, mention may be made, for example, of the chlorides of the following compounds:
4xe2x80x2,5,7-trihydroxyflavylium, commonly known as xe2x80x9capigeninidine chloridexe2x80x9d,
3xe2x80x2,4xe2x80x2,7-trihydroxyflavylium,
4xe2x80x2-hydroxyflavylium,
4xe2x80x2,7-dihydroxyflavylium,
3xe2x80x2,4xe2x80x2-dihydroxyflavylium,
3xe2x80x2,4xe2x80x2-dihydroxy-7-methoxyflavylium,
3xe2x80x2,4xe2x80x2,5,7-tetrahydroxyflavylium, and
3xe2x80x2,4xe2x80x2,5xe2x80x2,5,7-pentahydroxyflavylium.
For example, the at least one flavylium salt compound may be chosen from at least one of apigeninidine chloride (4xe2x80x2,5,7-trihydroxyflavylium chloride) and 3xe2x80x2,4xe2x80x2,7-tri-hydroxyflavylium chloride. These compounds can be prepared in pure form, i.e., in a form at least 90% pure.
According to certain embodiments, the present invention comprises using apigeninidine chloride in the form of, or derived from, a plant extract, which can be readily prepared by extraction and isolation from leaves of Sorghum caudatum according to, for example, at least one of the processes disclosed in patents CN 1,064,284A and CN 1,035,512C, the disclosures in both patents directed to said extraction and/or isolation are hereby incorporated by reference, and variants of these processes.
According to certain embodiments, the at least one flavylium salt compound may be chosen from those extracted from at least one of the stems, seeds, and leaves of Sorghum bicolour; the petals of Gesneria fulgens; and at least one of the species Blechum procerum and Sorghum in combination with Colletotrichum graminicola. 
According to certain embodiments, the present invention comprises using an extract from the leaves of Sorghum bicolour, which can be obtained by an aqueous-alcoholic extraction in acidic medium at an extraction temperature ranging from 30 to 40xc2x0 C. with a ratio of the volume of solvent to the mass of Sorghum bicolor leaves ranging from 10:1 to 30:1. The Sorghum plant extract can have an approximate titre ranging from 0.05% to 50% by weight of apigeninidine chloride.
The at least one flavylium salt compound which is unsubstituted in position 3 and which is substituted with at least one radical chosen from a hydroxyl radical and an alkoxy radical, may be readily and/or cheaply obtained by synthesis, for example, by the well-known method of R. Robinson and D. Pratt, J. Chem. Soc. 745 (1923), the disclosure of which directed to said synthesis is hereby incorporated by reference. The method comprises condensing at least one of an ortho-hydroxybenzaldehyde and a substituted ortho-hydroxybenzaldehyde with at least one of an acetophenone and a substituted acetophenone to yield, by selecting the substituents, a desired at least one flavylium salt compound, corresponding to formula (I).
Taking apigeninidine chloride (4xe2x80x2,5,7-trihydroxyflavylium chloride) as an example, the synthetic scheme (i) may be as follows: 
Taking 3xe2x80x2,4xe2x80x2,7-trihydroxyflavylium chloride as an example, the synthetic scheme (ii) may be as follows: 
A variety of synthetic routes, for example those that are well known in the field, may be used to lead to apigeninidine.
One method for preparing apigeninidine comprises, for example, in a first step, preparing trimethylapigeninidine by condensing commercial 4,6-dimethoxy-2-hydroxybenzaldehyde with commercial 4-methoxyacetophenone in an anhydrous ether medium at 0xc2x0 C., and saturating with anhydrous HCl, to yield, after filtration, an orange-red precipitate of trimethylapigeninidine. In a second step, the trimethylapigeninidine obtained in the preceding step is hydrolyzed to apigeninidine chloride, the reaction being carried out in a medium of HI and phenol and AgCl dissolved in methanol. Such a synthetic method is disclosed for example, by R. Robinson and A. Robertson in J. Chem. Soc. 1951 (1926) and 2196 (1927), the disclosure of which directed to said synthesis is incorporated herein by reference.
Another method, for example, for preparing apigeninidine comprises condensing 2,4,6-trihydroxybenzaldehyde with 4-hydroxyacetophenone at 0xc2x0 C. in an anhydrous solvent medium, for example ethyl acetate, and saturating with anhydrous HCl, to yield apigeninidine chloride. Such a method is disclosed, for example, by R. Robinson and A. Robertson in J. Chem. Soc. 1528 (1928), the disclosure of which directed to said synthesis is hereby incorporated by reference.
Another method, for example, for preparing apigeninidine chloride comprises reducing at least one of a flavone, naringenin, and triacetyl derivatives thereof, with NaBH4, and then oxidizing the product obtained with chloranil (tetrachloro-1,4-benzoquinone). The method is disclosed, for example, by J. G. Sweeny and G. A. Iacobucci in the review Tetrahedron 33 2923-2927 (1977), the disclosure of which directed to said synthesis is hereby incorporated by reference.
As a further example, use may be made of a method comprising condensing 2,4-dihydroxy-6-benzoyloxybenzaldehyde with 4-hydroxyacetophenone at 0xc2x0 C. in an anhydrous ethyl acetate medium, saturating with anhydrous HCl and then debenzoylating the product obtained with sodium hydroxide, to yield apigeninidine chloride in high yield, according to scheme (i) described above. The method is disclosed, for example, by R. Robinson and J. C. Bell in J. Chem. Soc. 813 (1934), the disclosure of which directed to said synthesis is hereby incorporated by reference.
The concentration of the at least one flavylium salt compound as described according to the present invention may range, for example, from about 0.0001% to 10%, for further example, from 0.001% to 5%, by weight relative to the total weight of the composition.
The monocarbonyl and polycarbonyl compounds may be chosen, for example, from isatin, alloxane, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, pyrazoline-4,5-dione derivatives as disclosed in patent application FR 2 466 492 and WO 97/35842, the disclosures of both of which related to such compounds are hereby incorporated by reference, dihydroxyacetone (DHA), 4,4-dihydroxypyrazolin-5-one derivatives as disclosed in patent application EP 903 342, the disclosure of which related to such compounds is hereby incorporated by reference. These self-tanning agents may be combined with direct dyes and indole derivatives.
In another embodiment of the invention, use will be made, for example, of dihydroxyacetone (DHA).
The monocarbonyl and polycarbonyl compounds are generally present in the composition according to the invention in an amount ranging, for example, from 0.1% to 10% by weight relative to the total weight of the composition, and for further example ranging from 0.2% to 8% by weight relative to the total weight of the composition.
The composition in accordance with the present invention may also comprise at least one conventional cosmetic adjuvant chosen, for example, from fatty substances, organic solvents, ionic thickeners, nonionic thickeners, softeners, antioxidants, free-radical scavengers, opacifiers, stabilizers, emollients, silicones, a-hydroxy acids, antifoams, moisturizers, vitamins, fragrances, preserving agents, surfactants, fillers, polymers, propellants, acidifying agents, basifying agents, colorants, and any other ingredient usually used in cosmetics and/or dermatology, for example, for manufacturing antisun compositions in the form of emulsions.
The fatty substances may be chosen from oils, waxes. The term xe2x80x9coilxe2x80x9d should be understood to indicate a compound which is liquid at room temperature. The term xe2x80x9cwaxxe2x80x9d should be understood to indicate a compound which is solid or substantially solid at room temperature and whose melting point is generally greater than 35xc2x0 C.
Oils which may be mentioned include mineral oils (paraffin); plant oils (sweet almond oil, macadamia oil, blackcurrent seed oil, jojoba oil); synthetic oils, for example perhydrosqualene, fatty alcohols, fatty acids, and fatty esters (for example the (C12-C15) alkyl benzoate sold under the trade name FINSOLV TN by the company Finetex, octyl palmitate, isopropyl lanolate, triglycerides including those of capric/caprylic acid), oxyethylenated fatty esters, oxypropylenated fatty esters, and ethers; silicone oils (cyclomethicone, polydimethylsiloxanes or PDMSs) and fluoro oils, and polyalkylenes.
Waxy compounds which may be mentioned include paraffin, carnauba wax, beeswax, and hydrogenated castor oil.
Among the organic solvents which may be mentioned are lower alcohols and polyols.
According to one embodiment, the composition according to the invention may comprise at least 5% by weight, relative to the weight of the composition, of at least one polyhydroxylated solvent. The solvent may be chosen from glycols and glycol ethers, for example ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol and diethylene glycol. For example, the composition according to the invention can comprisea mixture of at least three different polyhydroxylated solvents and as a further example a mixture comprising propylene glycol, butylene glycol and dipropylene glycol.
The thickeners may be chosen, for example, from crosslinked polyacrylic acids, modified guar gums, unmodified guar gums and celluloses, chosen from hydroxyprolyl guar gum, methylhydroxyethylcellulose and hydroxypropylmethylcellulose.
Needless to say, a person skilled in the art will take care to select the optional additional compound(s) mentioned above and/or the amounts thereof such that at least one advantageous property intrinsically associated with the combination in accordance with the invention is not, or is not substantially, adversely affected by the addition(s) envisaged.
The composition according to the invention may be prepared according to techniques that are well known to those skilled in the art, for example those intended for preparing oil-in-water and water-in-oil emulsions.
This composition may be, for example, in at least one form chosen from simple emulsions, complex (O/W, W/O, O/W/O and W/O/W) emulsions (such as creams and milks), gels, cream-gels, lotions, powders, solid tubes, aerosols, mousses, and sprays.
The composition according to the invention may, for example, be in a form chosen from an oil-in-water emulsion and a water-in-oil emulsion.
When it is an emulsion, the aqueous phase of this emulsion may comprise a nonionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol. 13, 238 (1965), FR 2 315 991 and FR 2 416 008), the disclosures of all of which related to such vesicular dispersions are hereby incorporated by reference.
Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term xe2x80x9caboutxe2x80x9d. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. The examples which follow are intended to illustrate the invention without, however, limiting its scope.